Abstract

Surface-modified CaCO₃ nanoparticles, synthesized through plasma-enhanced chemical vapor deposition (PECVD), were employed to improve lubricant additive technology for internal combustion engines via reduction and/or replacement of additives, such as zinc dialkyl dithiophosphate (ZDDP), in engine oil. Various oil formulations were prepared with functionalized CaCO₃ nanoparticles, in combination with ashless dialkyl dithiophosphate (DDP) and ZDDP at low concentrations of phosphorus. Tribological test results indicate synergistic interaction of functionalized CaCO₃ nanoparticles with ZDDP and DDP, providing enhanced friction and wear performance under boundary lubrication. A comparative study of the tribo-surfaces morphology and chemistry was assessed via atomic force microscopy and X-ray absorption near-edge spectroscopy. Improved wear protection by functionalized CaCO₃BM (borate and methacrylate coated) nanoparticles under boundary lubrication was attributed to the formation of calcium and boron-rich 50–80 nm thick tribofilms on the worn surfaces. XANES results revealed that plasma-functionalized CaCO₃ nanoparticles interact with ZDDP and DDP and participate in tribofilm formation through tribo-chemical reactions and metal cation supply to form stable and wear-resistant tribofilms. These results provide strong support for the potential application of plasma-functionalized CaCO₃ nano-additives to reduce the concentration of harmful P-based additives in automotive lubricants.

Graphical Abstract

中文翻译：

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血浆功能化的CaCO 3纳米粒子与锌和无灰二硫代磷酸盐添加剂的摩擦学相互作用

摘要

通过等离子体增强化学气相沉积（PECVD）合成的表面改性的CaCO ₃纳米颗粒，通过减少和/或更换发动机中的添加剂（例如二烷基二硫代磷酸锌（ZDDP））来改善内燃机的润滑油添加剂技术。油。用功能化的CaCO ₃纳米颗粒，以及低磷浓度的无灰二烷基二硫代磷酸酯（DDP）和ZDDP制备了各种油制剂。摩擦学测试结果表明功能化CaCO _3的协同相互作用具有ZDDP和DDP的纳米颗粒，在边界润滑下提供增强的摩擦和磨损性能。通过摩擦力显微镜和X射线吸收近缘光谱学评估了摩擦表面的形态和化学性质的比较研究。在边界润滑条件下，功能化的CaCO ₃ BM（涂覆有硼酸盐和甲基丙烯酸酯）纳米颗粒改善了磨损防护，这归因于在磨损表面上形成了富含钙和硼的50-80 nm厚的摩擦膜。XANES结果显示，血浆功能化的CaCO ₃纳米颗粒与ZDDP和DDP相互作用，并通过摩擦化学反应和金属阳离子供应参与摩擦膜的形成，从而形成稳定且耐磨的摩擦膜。这些结果为等离子体功能化的CaCO ₃纳米添加剂潜在的应用提供了有力的支持，以减少汽车润滑油中有害的P基添加剂的浓度。

图形概要